JPH06100628A - Polymer containing vinyl ether group and its production - Google Patents

Abstract

PURPOSE:To form a polymer containing vinyl ether groups by polymerizing a vinyl ether monomer of a specified formula and at least another monomer of a specified formula in the presence of a polymerization initiator. CONSTITUTION:A monomer of formula I wherein R<1> is H or methyl; and R<2> is 1-10C alkylene is polymerized with 1-40wt.% at least one monomer selected from among monomers of CX2=XR<4>Y and formulas III, IV and V wherein X is H or halogen, Y is phenyl, cyano, halogen, CO2R5, OCOR<6> or CON(R<6>)2; R<4> is 1-10 C alkyl, perfluoroalkyl, glycidyl, 3-10 C hydroxyalkyl, (CH2CH2Q)p-H or formula II; p is 0 or 1-5; a is 0, 1 or 2; R<6> is H or 1-5 C alkyl; R<7> to R<10> are each H or 1-10C alkyl; Z is oxygen or N-R<11>; and R<11> is H, phenyl, 1-10C alkyl or cycloalkyl in the presence of free-radical polymerization initiator to obtain a vinyl ether polymer of a number-average molecular weight of 500-1000000, represented by formula VI (wherein m is 1-10000; and n is 0-10000).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel vinyl ether group-containing polymer and a method for producing the same. More specifically, the present invention has a highly reactive cross-linking site branched from the polymer main chain, and therefore, a vinyl ether group-containing polymer which is suitable for a wide range of applications as it is or after being cross-linked, and this product. The present invention relates to an efficient manufacturing method.

[0002]

2. Description of the Related Art Polymer compounds having a branched reactive functional group have been attracting attention since they can be industrially applied to thermosetting resins. Among them, a polymer compound in which a vinyl ether group is pendantly branched from the main chain has been attracting attention in recent years as a cationic curable resin. On the other hand, the physical properties of acrylic resins can be easily adjusted by combining them with a wide variety of monomers to form copolymers.Therefore, polymer compounds in which the main chain is an acrylic resin and the vinyl ether group is branched from it are industrially widely used. Highly effective and useful. However, since the monomer necessary to obtain such a polymer compound has two vinyl groups in one molecule, ordinary radical polymerization does not produce a linear polymer compound, but a high-molecular compound having a cross-linked three-dimensional structure. It has been reported to become a molecular compound.
Conventionally, as a method for selectively homopolymerizing a vinyl group on the (meth) acrylate side, anionic polymerization with potassium amide has been proposed [German Patent Nos. 1027401 and 1034363 (1958)]. However, anionic polymerization is an extremely sensitive polymerization method for water, carbon dioxide, etc., and is not industrially suitable,
Under the present circumstances, development of various polymers having a vinyl ether group and a method for producing the same is strongly desired.

[0003]

Under these circumstances, the present invention is directed to a novel polymer in which the main chain is an acrylic resin and a vinyl ether group which is a reactive functional group is branched from the acrylic resin, and this polymer. The present invention has been made for the purpose of providing a method for industrially easily producing.

[0004]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that by polymerizing a monomer having a specific structure under specific conditions, the main chain of the polymer is changed to a vinyl ether group. It was found that a novel vinyl ether group-containing polymer that was branched was obtained in a short time with high yield and easily, and without using a special device, and based on this finding, the present invention was completed. .
That is, the present invention has the general formula

[0005]

[Chemical 10]

[Wherein R ¹ is a hydrogen atom or a methyl group, and R ^{2 is}
Is an alkylene group having 1 to 10 carbon atoms, and m is 1 to 10000.
, N is 0 or an integer of 1 to 10,000, but R
² is - (CH _{2) 2} - when n is an integer from 1 to 10000, R ³ is CX ₂ -CR ⁴ Y,

[0007]

[Chemical 11]

Or

[0009]

[Chemical 12]

A group represented by, X is a hydrogen atom or a halogen atom, Y is a phenyl group, a cyano group, a halogen atom, CO
₂ R ⁵ , OCOR ⁶ or CON (R ⁶ ) ₂ , R ⁴ is a hydrogen atom, a methyl group or CH ₂ CO ₂ R ⁶ , R ⁵ is an alkyl group or a perfluoroalkyl group having 1 to 10 carbon atoms, a glycidyl group, carbon A hydroxyalkyl group of the number 3 to 10, (CH ₂ C
H ₂ ) _P- H or

[0011]

[Chemical 13]

A group represented by, p is 0 or an integer of 1 to 5,
q is 0, 1 or 2, R ⁶ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Z is Oxygen atom or NR ¹¹ , R ¹¹ is a hydrogen atom, a phenyl group, or a carbon number of 1 to 1.
An alkyl group of 0 or a cycloalkyl group of 1 to 10 carbon atoms] 500 to 100,000
0 vinyl ether group-containing polymer. According to the present invention, the vinyl ether group-containing polymer has the general formula

[0013]

[Chemical 14]

(Wherein R ¹ and R ² have the same meanings as described above), or the monomer represented by the general formula [2] and the general formula CX ₂ = CR ⁴ Y ... [3 ] (Wherein X, Y and R ⁴ have the same meaning as described above), or a general formula

[0015]

[Chemical 15]

A monomer represented by the formula (wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meanings as described above), or a general formula

[0017]

[Chemical 16]

A monomer represented by the formula (wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meanings as described above), or a general formula

[0019]

[Chemical 17]

A monomer represented by the formula (Z has the same meaning as described above) is added at a concentration of 1 to 40 in the total monomer system.
It can be produced by polymerizing in the presence of a radical polymerization initiator so as to be used in a weight percentage. Hereinafter, the present invention will be described in detail.

The vinyl ether group-containing polymer of the present invention has a structure represented by the above general formula [1], and when m or n in the formula exceeds 10,000, the viscosity of the obtained polymer becomes high. However, it is not preferable because the workability is lowered. Further, when the carbon number of R ² is 1, the compound obtained has an acetal structure and tends to be extremely susceptible to hydrolysis. On the other hand, when the carbon number of R ² exceeds 10, the proportion of the vinyl ether group contained in the obtained polymer decreases, and thus it is generally not preferable for efficiently exhibiting the effect of the vinyl ether group. Further, if the number average molecular weight of the polymer exceeds 1,000,000, the viscosity becomes high and the workability is deteriorated, which is not preferable. The vinyl ether group-containing polymer of the present invention is a vinyl ether group-containing monomer represented by the general formula [2], or a vinyl ether group-containing monomer represented by the general formula [2] and a monomer represented by the general formula [3] or general. It is obtained by polymerizing the monomer represented by the formula [4], the monomer represented by the general formula [5], or the monomer represented by the general formula [6] in the presence of a polymerization initiator. Examples of the vinyl ether group-containing monomer represented by the general formula [2] include 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl ( (Meth) acrylate, 5
-Vinyloxypentyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 7-vinyloxyheptyl (meth) acrylate, 8-vinyloxyoctyl (meth) acrylate, 9-vinyloxynonyl (meth) acrylate, 10-vinyl Roxydecanyl (meta)
Acrylate can be preferably mentioned.

Examples of the comonomer represented by the above general formulas [3], [4], [5] and [6] include, for example, methyl (meth) acrylate, ethyl (meth) acrylate and propyl ( (Meth) acrylate, butyl (meth) acrylate, isobutyl (meth)
Acrylate, sec-butyl (meth) acrylate,
Alkyl (meth) such as pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate Acrylate, trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, heptylfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluoroisobutyl (meth) acrylate, perfluoro-sec-butyl (meth) acrylate, Perfluoropentyl (meth) acrylate, perfluorohexyl (meth) acrylate, perfluoroheptyl (meth) acrylate, perfluorooctyl (meth Acrylate, perfluoro-2-ethylhexyl (meth) acrylate, perfluorononyl (meth) acrylate, perfluoroalkyl (meth) acrylate such as perfluorodecyl (meth) acrylate, vinyl acetate, methyl itaconate, ethyl itaconate, propyl itaconate, Isopropyl itaconic acid, butyl itaconic acid, isobutyl itaconic acid, sec-butyl itaconic acid, t-butyl itaconic acid, pentyl itaconic acid, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth)
Acrylate, epoxy group-containing (meth) acrylate such as 5- (3,4-epoxycyclohexylmethyloxacarbonyl) pentyl (meth) acrylate, 2-
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) Acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyheptyl (meth) acrylate, hydroxyoctyl (meth)
Acrylate, hydroxy nonyl (meth) acrylate, hydroxy decyl (meth) acrylate, polyethylene glycol monomethacrylate _{[CH 2 = C (CH 3} )
_{CO 2 (CH 2 CH 2 O} ) n -H, n = 2~5], polyethylene glycol monoacrylate [CH ₂ = CHCO ₂ (C
H ₂ CH ₂ O) _n —H, n = 2 to 5], a hydroxy group-containing (meth) acrylate, (meth) acrylic acid, styrene, α-methylstyrene, (meth) acrolein,
(Meth) acrylonitrile, (meth) acrylamide,
N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N, N-diisopropyl (meth)
(Meth) acrylamide derivatives such as acrylamide, N, N-dibutyl (meth) acrylamide, N, N-dipentyl (meth) acrylamide, fumaric acid, dimethyl fumarate, diethyl fumarate, dipropyl fumarate,
Diisopropyl fumarate, dibutyl fumarate, diisobutyl fumarate, disec-butyl fumarate, di-t-butyl fumarate, dipentyl fumarate, dihexyl fumarate, diheptyl fumarate, dioctyl fumarate, dinonyl fumarate, didecyl fumarate, Alternatively, monoesters of the aforementioned fumaric acid derivatives, asymmetric esters, maleic acid, dimethyl maleate, diethyl maleate, dipropyl maleate, diisopropyl maleate, dibutyl maleate, diisobutyl maleate, di s maleate.
ec-Butyl, di-t-butyl maleate, dipentyl maleate, dihexyl maleate, diheptyl maleate, dioctyl maleate, dinonyl maleate, didecyl maleate, maleic anhydride, maleimide, N-methylmaleimide, N-ethylmaleimide. , N-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, N-sec-
Butyl maleimide, Nt-butyl maleimide, N-pentyl maleimide, N-hexyl maleimide, N-heptyl maleimide, N-octyl maleimide, N-nonyl maleimide, N-decyl maleimide, N-cyclopentyl maleimide, N-cyclohexyl maleimide, Preferable examples include N-cycloheptylmaleimide and N-phenylmaleimide.

Further, as the radical polymerization initiator used for producing the polymer of the present invention, for example, m-diisopropylbenzene monohydroperoxide, p-
Diisopropylbenzene monohydroperoxide, t
-Butyl hydroperoxide, diisopropylcyclohexyl hydroperoxide, isopropylcyclohexyl hydroperoxide, p-menthane hydroperoxide, 1,3,5-trimethylcyclohexyl hydroperoxide, 1,3,4-trimethylcyclohexyl hydroperoxide, diisopropyl Benzene hydroperoxide, 2,4,4-trimethylpentane-2
-Hydroperoxide, 2,5-dimethylhexane-
2,5-dihydroperoxide, cumene hydroperoxide, 2,5-dimethyl-2,5-di (t-hexylperoxy) hexane, dicumyl peroxide, t-hexyl-α-cumyl peroxide, t -Amyl-α-cumyl peroxide, 2,5-dimethyl-2,5-di (t-
Butylperoxy) hexane, 1,1'-di-t-peroxy-1,1'-dicyclohexylacetylene, t-butyl-α-cumyl peroxide, 2,5-dimethyl-2,5
-Di (t-hexylperoxy) hexyne-3, di-t
-Butyl peroxide, 3,6-dimethyl-3,6-di (t-butylperoxy) octyne-4,2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-
3,2-ethylhexanoyl peroxide, α-chloropropinoyl peroxide, 2-ethylbutyryl peroxide, 2-methylpentanoyl peroxide, isobutyryl-2-ethylhexanoyl peroxide, α-bromopropionyl peroxide, Isobutyryl peroxide, n-butyryl-2-ethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, o-
Chlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, o-methylbenzoyl peroxide, 2-butenoyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, n-butyryl peroxide , Stearoyl peroxide, propionyl peroxide, propionyl-n-butyryl peroxide, 3,3-dimethylbutyryl peroxide, succinic acid peroxide, n-butyrylacetyl peroxide, propionylbenzoyl peroxide, acetylcyclohexylsulfonyl peroxide, t -Butyl peroxy neodecanoate, t-butyl peroxy neo heptanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate,
2,5-Dimethyl-2,5-di (2-ethylhexylperoxy) hexane, 2,5-dimethyl-2,5-di (2-
Ethylbutyrylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (isobutyrylperoxy) hexane,
t-butylperoxy-2-ethylhexanoate, t
-Butyl peroxydiethyl acetate, t-hexyl peroxyisobutyrate, t-butyl peroxy-2
-Methylpentanoate, t-butylperoxy-2-
Methyl butyrate, t-butyl peroxyisobutyrate, t-hexyl peroxy-o-methyl benzoate, t-hexyl peroxy-3,5,5-trimethylhexanoate, t-hexyl peroxy laurate, t
-Butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-
Butyl peroxy crotonate, t-butyl peroxy-n-octoate, t-butyl peroxy laurate, di-t-butyl peroxyazelate, t-butyl peroxy n-decanoate, 2,5-dimethylhexane-2 , 5-diperoxybenzoate, t-hexylperoxybenzoate, t-butylperoxyisovalerate, t-hexylperoxy-p-chlorobenzoate, t-butylperoxyacetate, t-butylperoxy-p- t-butylbenzoate, t-butylperoxy-p-methylbenzoate, t-butylperoxybenzoate, di (t-butyl) peroxyphthalate, t-butylperoxy-3-hydroxypropionate, t-butylper Oxy-2,4-dichlorobenzoate, mono-t- Cylperoxyphthalic acid, mono-t-butylperoxysuccinic acid, t-hexylperoxy-n-butyl carbonate, t-hexylperoxy-2-ethylhexyl carbonate, t-hexylperoxyisopropyl carbonate, t-butylper Oxyisopropyl carbonate, t-butylperoxy-sec-butyl carbonate, t-butylperoxycyclohexyl carbonate, t-butylperoxy-n-propyl carbonate, t-butylperoxyisobutyl carbonate, t-butylperoxyisoamyl carbonate, t-butylperoxy-n-hexyl carbonate, t-butylperoxy-n-dodecyl carbonate, t-butylperoxy-2-ethylhexyl carbonate, t-butylperoxy- -Butyl carbonate, t-butyl peroxyethyl carbonate, diethylene bis (t-butyl peroxy carbonate), t-butyl peroxymethyl carbonate, ethylene bis (t-butyl peroxy carbonate), diethyl peroxy dicarbonate, di- n-butyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, dibenzyl peroxydicarbonate, di-n-
Propyl peroxydicarbonate, didodecyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-4-t-butylcyclohexyl peroxydicarbonate, diisobutyl peroxydicarbonate, diethyl carbitol peroxydicarbonate, dimethyl peroxydicarbonate Carbonate, dimethyl carbitol peroxydicarbonate, dibutyl carbitol peroxydicarbonate, diethoxyethyl peroxydicarbonate, dibutoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate , Dimethoxyethyl peroxydicarbonate, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis ( - hexyl peroxy) -3,
3,5-trimethylcyclohexane, 1,1-bis (t-
Butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-hexylperoxy) heptane, 2,2-bis- (t -Hexylperoxy) butane, 2,2-bis (t-butylperoxy) -5-methylhexane, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-hexylperoxy) ) Propane, n-butyl-4,4-bis (t-butylperoxy) valerate, cyclohexyl-4,4-bis (t
-Butylperoxy) valerate, 2,2-bis (t
-Butylperoxy) propane, α, α-bis (t-butylperoxy) toluene, isoamyl-3,3-bis (t-butylperoxy) butyrate, benzyl-3,
Organic peroxide such as 3-bis (t-butylperoxy) butyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, or 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile),
2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionitrile) (AIBN), 2,2'-azobis (2-methylbutyronitrile), 1 , 1'-Azobis (cyclohexane-1
-Carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamide, 2-phenylazo-4-
Methoxy-2,4-dimethylvaleronitrile, 2,2'-
Azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2′-azobis [N- (4-chlorophenyl) -2-methylpropionamidine] dihydrochloride,
2,2'-azobis [N- (4-hydroxyphenyl)-
2-Methylpropionamidine] dihydrochloride, 2,2′-azobis [2-methyl-N- (phenylmethyl) -propionamidine] dihydrochloride, 2,2′-azobis [2-methyl-N- (2 -Propenyl) propionamidine] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride Hydrochloride, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane ]
Dihydrochloride, 2,2'-azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride, 2,2'-azobis [2 -(3,4,
5,6-Tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloric acid Salt, 2,2'-azobis [2- [1
-(2-Hydroxyethyl) -2-imidazoline-2-
Iyl] propane] dihydrochloride, 2,2′-azobis [2-
(2-Imidazolin-2-yl) propane] dihydrochloride,
2,2'-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide], 2,2'-azobis [2-methyl-N-
[1,1-Bis (hydroxymethyl) ethyl] propionamide], 2,2′-azobis [2-methyl-N- (2
-Hydroxyethyl) propionamide], 2,2'-azobis (2-methylpropionamide) dihydrate, 2,
2'-azobis (2,4,4-trimethylpentane), 2,
2'-azobis (2-methylpropane), dimethyl 2,
2'-azobis (2-methylpropionic acid), 4,4'-
Azobis (4-cyanovaleric acid), 2,2'-azobis [2
Preferred examples include azo initiators such as-(hydroxymethyl) propionitrile].

In the present invention, the concentration of all the monomers in the system at the time of polymerization is selected in the range of 1 to 40% by weight. If this concentration exceeds 40% by weight, a polymerization reaction takes place in the vinyl ether group, and gelation of the produced polymer is extremely likely to occur, making it difficult to obtain the desired polymer represented by the general formula [1]. On the contrary, when it is less than 1% by weight, the polymerization efficiency is poor and it is not industrial. The amount of the radical polymerization initiator added to the monomer is preferably 0.1.
It is selected in the range of 01 to 10% by weight, more preferably 0.05 to 5% by weight. If this amount is less than 0.01% by weight, the yield of the produced polymer is low, and if it exceeds 10% by weight, a radical terminating reaction is likely to occur and the molecular weight of the target polymer tends to be low. Further, the polymerization temperature is 0 to
160 degreeC is preferable and 20-140 degreeC is especially preferable.
If this temperature is lower than 0 ° C, the polymerization reaction tends not to proceed smoothly, and if it exceeds 160 ° C, the vinyl ether group tends to react during the polymerization reaction, which is not preferable. The reaction time at this time is preferably 1 to 20 hours, particularly preferably 3 to 10 hours. If the reaction time is less than 1 hour, the polymerization reaction does not proceed sufficiently, and if it exceeds 20 hours, the conversion rate of the monomer in the polymerization reaction tends not to increase. The target vinyl ether group-containing polymer can be produced by any of the solution method, the emulsification method and the suspension method as the polymerization method in the invention.

[0025]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Example 1 500 ml equipped with stirrer, reflux tube, thermometer, nitrogen inlet
Benzene 246 g, methyl methacrylate (MMA) 5 g, 2-vinyloxyethyl methacrylate (2-VEM) 7.3 g, perbutyl ND [trade name: manufactured by NOF CORPORATION] 180 mg were charged to a 4-necked flask at 55 ° C. Then, the temperature was maintained for 6 hours to carry out the polymerization reaction. After the reaction was completed, the solvent benzene was distilled off under reduced pressure, and 2000 ml of it was removed.
A white precipitate was obtained by reprecipitation in n-hexane. By drying this white precipitate under reduced pressure, the target methyl methacrylate represented by the following structural formula and 2-
A copolymer of vinyloxyethyl methacrylate was obtained as a colorless solid (9.2 g, yield 72%). Table 1 shows the average molecular weight of the polymer compound obtained by reprecipitation, the dispersion ratio, the peak position of ¹ H-NMR, the copolymerization ratio obtained from the integrated value of the peak, and the main absorption of IR.

[0026]

[Chemical 18]

(Copolymerization ratio x: y = 41: 59) Examples 2 to 5 Instead of perbutyl ND, which is the polymerization initiator in Example 1, perbutyl PV [trade name: manufactured by NOF Corporation],
Perloyl IPP [Product name: NOF Corporation], Niper BW [Product name: NOF Corporation], Perbutyl Z [Product name: NOF Corporation] (Toluene instead of benzene as solvent Used) and a polymerization reaction temperature of 6
The same procedure as in Example 1 was repeated except that the temperatures were changed to 5 ° C, 50 ° C, 80 ° C, and 110 ° C, respectively. Yield of polymer compound obtained by reprecipitation, average molecular weight, dispersion ratio, ¹ H-N
Table 1 shows the peak position of MR, the copolymerization ratio obtained from the integrated value of the peak, and the main absorption of IR. The basic structure of each polymer is the same as that of Example 1, and the copolymerization ratio x:
The value of y is 39:61 in Example 2 and 2: 9 in Example 3.
8, Example 4 was 24:76, and Example 5 was 17:83. Examples 6 and 7 The same procedure as in Example 1 was carried out except that the charged amount of the monomer in Example 1 was changed as shown in Table 1. Yield of polymer compound obtained by reprecipitation, average molecular weight, dispersion ratio, ¹ H-N
Table 1 shows the peak position of MR, the copolymerization ratio obtained from the integrated value of the peak, and the main absorption of IR. The basic structure of each polymer is the same as that of Example 1, and the copolymerization ratio x:
The value of y was 17:83 in Example 6 and 6:94 in Example 7.
Met.

Examples 8 to 10 The procedure of Example 1 was repeated, except that the amount of the initiator charged was changed as shown in Table 1. Yield of polymer compound obtained by reprecipitation, average molecular weight, dispersion ratio,
Table 1 shows the peak position of ¹ H-NMR, the copolymerization ratio obtained from the integrated value of the peak, and the main absorption of IR. The basic structure of each polymer was the same as in Example 1, and the copolymerization ratio x: y was 39:61 in Example 8, 42:58 in Example 9, and 40:60 in Example 10. there were. Example 11 190.0 g of benzene, 10.0 g of 2-vinyloxyethyl methacrylate, and perbutyl ND were placed in a 30 ml four-necked flask equipped with a stirrer, a reflux tube, a thermometer, and a nitrogen inlet.
[Brand name: manufactured by Nippon Oil & Fats Co., Ltd.] 141 mg was charged and heated to 55 ° C., and the temperature was maintained for 6 hours to carry out a polymerization reaction. After completion of the reaction, the solvent benzene was distilled off under reduced pressure to obtain 28 wt.
A white precipitate was obtained by reprecipitation in 2000 ml of methanol to which 50 mg of a methanol solution of sodium methoxide was added. By drying this white precipitate under reduced pressure, 6.2 g (yield 62%) of a target copolymer of methyl methacrylate and 2-vinyloxyethyl methacrylate represented by the following structural formula was obtained as a colorless solid. Average molecular weight of polymer compound obtained by reprecipitation, dispersion ratio, ¹
Table 1 shows the peak position of H-NMR, copolymerization ratio, and main absorption of IR.

[0029]

[Chemical 19]

[0030]

[Table 1]

[0031]

[Table 2]

Note) Perbutyl ND: Trade name [NOF
Perbuyl PV: Product name [Nippon Oil & Fats Co., Ltd.] Perloyl IPP: Product name [Nippon Oil and Fats Co., Ltd.] Niper BW: Product name [Nippon Yushi Co., Ltd.] Perbutyl Z: Product name [ Made by Nippon Oil & Fat Co., Ltd.]

Comparative Example 1 500 ml equipped with a stirrer, a reflux tube, a thermometer and a nitrogen inlet.
123 g of benzene, 40.7 g of methyl methacrylate, 59.4 g of 2-vinyloxyethyl methacrylate, perbutyl ND in a 4-necked flask of No. [trade name: NOF CORPORATION]
[Preparation] 1.5 g was charged and heated to 55 ° C., and the polymerization reaction was carried out while maintaining the temperature. Gelation occurred 2 hours after the reaction started. Comparative Example 2 500 ml equipped with stirrer, reflux tube, thermometer, nitrogen inlet
123 g of benzene, 72 g of methyl methacrylate, 28 of 2-vinyloxyethyl methacrylate in a 4-necked flask.
g, perbutyl ND [trade name: manufactured by NOF CORPORATION] 1.5 g
Was charged and heated to 55 ° C., and the polymerization reaction was carried out while maintaining the temperature. Gelation occurred 3 hours after the reaction started. Comparative Example 3 300 ml equipped with stirrer, reflux tube, thermometer, nitrogen inlet
100 g of benzene, 100 g of 2-vinyloxyethyl methacrylate, and 1.4 g of perbutyl ND [trade name: manufactured by NOF CORPORATION] were charged into a 4-necked flask and heated to 55 ° C.
The temperature was maintained and the polymerization reaction was carried out. Gelation occurred 2 hours after the reaction started.

[0034]

INDUSTRIAL APPLICABILITY The vinyl ether group-containing polymer of the present invention is a novel compound and has a highly reactive crosslinking site branched from the polymer main chain. For intermediate raw materials, resins and their raw materials, biomaterials, electronic materials, optical materials, surfactant materials, sliding materials, heat resistant materials, reactive diluents, paints and inks It is preferably used for raw materials, adhesives, raw materials thereof, molded products and the like. In addition, the production method of the present invention makes it possible to produce a vinyl ether group-containing polymer in a short time with a high yield and easily without using a special apparatus.

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[Procedure amendment]

[Submission date] February 5, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Chemical 1] [In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is a carbon atom 1
An alkylene group of 10 to 10, m is an integer of 1 to 10,000, and n
Is 0 or an integer of 1 to 10000, but R ² is-(C
When H ₂ ) ₂ −, n is an integer of 1 to 10000,
R ³ is _CX 2 ^-CR 4 Y,

[Chemical 2] Or

[Chemical 3] A group represented by, X is a hydrogen atom or a halogen atom, Y is a phenyl group, a cyano group, a halogen atom, CO ₂ R ⁵ , or OC.
OR ⁶ or ^{_{CON (R 6) 2, R}} 4 is a hydrogen atom, a methyl group or ^{_{CH 2 CO 2 R 6, R}} 5 is an alkyl group or perfluoroalkyl group having 1 to 10 carbon atoms, a glycidyl group, 3 to 10 carbon atoms Hydroxyalkyl group of (CH ₂
CH ₂ O) _P- H or

[Chemical 4] A group represented by, h is 0 or an integer of 1 to 5, q is 0, 1 or 2, R ⁶ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Z is an oxygen atom or N—R.
¹¹ , R ¹¹ is a hydrogen atom, a phenyl group, or a carbon number of 1 to 10.
Is an alkyl group or a cycloalkyl group having 1 to 10 carbon atoms].
Polymers containing vinyl ether groups.

[Chemical 5] (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a carbon atom 1
10 is an alkylene group of 10), or a monomer represented by the general formula [2] and the general formula CX ₂ ═CR ⁴ Y ... [3] [wherein X is a hydrogen atom or a halogen atom] , Y is a phenyl group, a cyano group, a halogen atom, CO ₂ R ⁵ , OCOR ⁶
Or _{^{CON (R 6) 2, R}} 4 is a hydrogen atom, a methyl group or _{^{CH 2 CO 2 R 6, R}} 5 is an alkyl group or perfluoroalkyl group having 1 to 10 carbon atoms, a glycidyl group, hydroxy C3-10 Alkyl group, (CH ₂ CH
₂ O) _P- H or

[Chemical 6] A group represented by, p is an integer of 0 or 1 to 5, q is 0, 1 or 2, R ⁶ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, or a general formula

[Chemical 7] (Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), or a general formula

[Chemical 8] (Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), or a general formula

[Chemical 9] (Wherein Z is an oxygen atom or N—R ¹¹ , and R ¹¹ is a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 1 to 10 carbon atoms). The method for producing a vinyl ether group-containing polymer according to claim 1, wherein the polymerization is carried out in the presence of a radical polymerization initiator such that the total monomer concentration in the system is 1 to 40% by weight.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

A group represented by, X is a hydrogen atom or a halogen atom, Y is a phenyl group, a cyano group, a halogen atom, CO
₂ R ⁵ , OCOR ⁶ or CON (R ⁶ ) ₂ , R ⁴ is a hydrogen atom, a methyl group or CH ₂ CO ₂ R ⁶ , R ⁵ is a carbon atom
An alkyl group of 10 to a perfluoroalkyl group,
Glycidyl group, a hydroxyalkyl group having 3 to 10 carbon _{atoms, (CH 2 CH 2 O)} P -H or

Claims (2)

[Claims] 1. A general formula:[R in the formula¹Is a hydrogen atom or a methyl group, R²Has 1 to 1 carbon atoms
10 alkylene groups, m is an integer from 1 to 10000, n is
0 or an integer of 1 to 10,000, but R²Is-(C
H₂)₂In the case of −, n is an integer of 1 to 10000, and R³
Is CX₂-CR^FourY,OrA group represented by, X is a hydrogen atom or a halogen atom, and Y is a fluorine atom.
Phenyl group, cyano group, halogen atom, CO₂R^Five, OCO
R⁶Or CON (R⁶)₂, R^FourIs a hydrogen atom, a methyl group or C
H₂CO₂R⁶, R^FiveIs an alkyl group having 1 to 10 carbon atoms
Is a perfluoroalkyl group, glycidyl group, carbon number 3 to
10 hydroxyalkyl groups, (CH₂CH ₂)_P-H orA group represented by, p is 0 or an integer of 1 to 5, q is 0, 1, or
Is 2, R⁶Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R⁷, R⁸, R⁹And R^TenIs hydrogen atom or carbon number
1 to 10 alkyl groups, Z is an oxygen atom or NR¹¹, R
¹¹Is hydrogen atom, phenyl group, alkyl having 1 to 10 carbon atoms
A group or a cycloalkyl group having 1 to 10 carbon atoms]
With a number average molecular weight of 500 to 1,000,000
Ether group-containing polymer. 2. A general formula: (In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is a carbon atom of 1 to
10 is an alkylene group), or the monomer represented by the general formula [2] and the general formula CX ₂ ═CR ⁴ Y ... [3] [wherein X is a hydrogen atom or a halogen atom, Y is a phenyl group, a cyano group, a halogen atom, CO ₂ R ⁵ , OCOR ⁶ or CON (R ⁶ ) ₂ , and R ⁴ is a hydrogen atom, a methyl group or CH ₂ C.
O ₂ R ⁶ and R ⁵ are alkyl groups having 1 to 10 carbon atoms, perfluoroalkyl groups, glycidyl groups, and 3 to 10 carbon atoms.
Hydroxyalkyl _{group, (CH 2 CH 2 O)} P -H or embedded image A group represented by, p is 0 or an integer of 1 to 5, q is 0, 1 or 2, and R ⁶ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms], or a general formula: Chemical 7] (Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), or a monomer represented by the general formula: (In the formula, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), or a monomer represented by the general formula: (Z in the formula is an oxygen atom or NR ¹¹ , R ¹¹ is a hydrogen atom,
Phenyl group, C1-10 alkyl group or C1
A cycloalkyl group of 10) is used so that the concentration of all monomers in the system is 1 to 40% by weight, and the polymerization is performed in the presence of a radical polymerization initiator. The method for producing a vinyl ether group-containing polymer according to claim 1.